Total synthesis of avenaol

• 安井, 基博

• 太田, 里奈

• 塚野, 千尋

• 竹本, 佳司

抄録

Avenaol, isolated from the allelopathic plant black oat, was the first C20 germination stimulant related to strigolactones. Structurally, it consisted of a bicyclo[4.1.0]heptanone skeleton containing a cyclopropane ring bearing three main chains projecting in the same direction (i.e. all-cis-substituted cyclopropane). Herein, we report the total synthesis of avenaol using a robust strategy involving the formation of an all-cis-substituted cyclopropane via an alkylidenecyclopropane. The key factors in the success of this total synthesis include the Rh-catalysed intramolecular cyclopropanation of an allene, an Ir-catalysed stereoselective double-bond isomerisation, and the differentiation of two hydroxymethyl groups via the regioselective formation and oxidation of a tetrahydropyran based on the reactivity of a cyclopropyl group. This strategy effectively avoids the undesired ring opening of the cyclopropane ring and the formation of a caged structure. Furthermore, this study confirms the proposed structure of avenaol, including its unique all-cis-substituted cyclopropane moiety.

収録刊行物

• Nature Communications

  Nature Communications 8 674-, 2017-09-22

  Springer Nature

キーワード

• Homogeneous catalysis
• Synthetic chemistry methodology
• Natural product synthesis

詳細情報

• CRID: 1050001335851968256
• NII論文ID: 120006366783
• ISSN: 20411723
• DOI: 10.1038/s41467-017-00792-1
• HANDLE: 2433/228128
• Web Site: https://www.nature.com/articles/s41467-017-00792-1.pdf
• Web Site: https://www.nature.com/articles/s41467-017-00792-1
• 本文言語コード: en
• 資料種別: journal article
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